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For this linchpin, the initial nucleophilic addition proceeds under Felkin\u2013Anh control to generate the syn-alkoxide, which undergoes a 1,4-Brook rearrangement to relay the negative charge, thus leading to the formation of a dithiane-stabilized carbanion. Subsequent trapping with an electrophile furnishes a tricomponent adduct with an embedded propionate subunit, a ubiquitous structural motif found in polyketides. The utility of this new linchpin is demonstrated with the construction of a potential C16\u2013C29 fragment for the synthesis of rhizopodin, an actin-binding macrolide.<\/jats:p>","DOI":"10.1021\/acs.orglett.5b03235","type":"journal-article","created":{"date-parts":[[2015,12,7]],"date-time":"2015-12-07T15:16:53Z","timestamp":1449501413000},"page":"6242-6245","source":"Crossref","is-referenced-by-count":17,"title":["An Effective Bifunctional Aldehyde Linchpin for Type\nII Anion Relay Chemistry: Development and Application to the Synthesis\nof a C16\u2013C29 Fragment of Rhizopodin"],"prefix":"10.1021","volume":"17","author":[{"given":"Bruno","family":"Melillo","sequence":"first","affiliation":[{"name":"University of Pennsylvania , , 231 South 34th Street , , ,","place":["Philadelphia, Pennsylvania, United States, 19104"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ming Z.","family":"Chen","sequence":"additional","affiliation":[{"name":"University of Pennsylvania , , 231 South 34th Street , , ,","place":["Philadelphia, Pennsylvania, United States, 19104"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Roberto","family":"Forestieri","sequence":"additional","affiliation":[{"name":"University of Pennsylvania , , 231 South 34th Street , , ,","place":["Philadelphia, Pennsylvania, United States, 19104"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"suffix":"III","given":"Amos B.","family":"Smith","sequence":"additional","affiliation":[{"name":"University of Pennsylvania , , 231 South 34th Street , , ,","place":["Philadelphia, Pennsylvania, United States, 19104"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2015,12,7]]},"reference":[{"key":"2026090111032042400_cit1a","volume-title":"The Polyketide\nMetabolites","author":"O\u2019Hagan","year":"1991"},{"key":"2026090111032042400_cit1b","doi-asserted-by":"publisher","first-page":"1","DOI":"10.1039\/np9951200001","volume":"12","author":"O\u2019Hagan","year":"1995","journal-title":"Nat. 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